EP2024471A2 - Gear lubricant with a base oil having a low traction coefficient - Google Patents
Gear lubricant with a base oil having a low traction coefficientInfo
- Publication number
- EP2024471A2 EP2024471A2 EP07760200A EP07760200A EP2024471A2 EP 2024471 A2 EP2024471 A2 EP 2024471A2 EP 07760200 A EP07760200 A EP 07760200A EP 07760200 A EP07760200 A EP 07760200A EP 2024471 A2 EP2024471 A2 EP 2024471A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- base oil
- lubricant
- gear lubricant
- gear
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/02—Mixtures of base-materials and thickeners
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/002—Traction fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- This invention is directed to lubricant base oils, and finished lubricants made from them, ha ⁇ ing very iow traction coefficients.
- gear lubricants having low ratios of Brookfield viscosity to kinematic viscosity a£ 100°C using polyalphaolellns, or combinations of " petroleum derived base oils with significant levels of viscosity index improver.
- Chevron Tegra ⁇ Syrthetic Gear Lubricant SAE 80W- 140 is made with highly refined petroleum derived Group ill base oil and greater than " 20 wt% viscosity index improver.
- Chevron Tegra® Synthetic Gear Lubricant SAE 75W-90 is made with polyalphaoiefin and diesler base oils. Tegra® is a registered trademark of Chevron Corporation. Polyalphaoiefin base oils are expensive and have less desired elastomer compatibility than ether base oils. Diester base oil provides improved elastomer compatibility and additive solubility, but is also very expensive and available in limited quantities.
- 20050258078, 20050261145, 20050261146, and 20050261 147 disclose that blends of base oils made from highly paraffinic wax with Group Ii or Grcnip III base oils will have very low Brookfield viscosities.
- Commonly assigned U.S. Patent Application Publication No. 20050241990 discloses that wormgear lubricants may be made using base oils Slaving a low traction coefficient made from a waxy feed.
- Commonly assigned U.S. Patent Application Publication No. 20050098476 discloses pour point depressing base oil blending components made by hydroisomerization dewaxing a waxy feed and selection of a heavy distillation bottoms product.
- a gear lubricant is desired having a higher kinematic viscosity at 100°C and lower Brookfield Ratio than the gear lubricants previously made.
- the gear lubricant will have a kinematic viscosity greater than 10 cSt at 100°C : and will also have a low Brookfield viscosity relative to kinematic viscosity; and a process to make if is also desired.
- Ae gear lubricant will also not require high amounts of viscosity index improver.
- a gear lubricant comprising a Fischer-Tropsch derived base oil having a VI greater than 150 and a traction coefficient less than 0.0 i 5 when measured at a kinematic viscosity of 15 cSt and at a slide to roil ratio of 40%.
- a Fischer-Tropsch derived base oil having a traction coefficient less than 0.015 when measured at 15 cSt and at a slide to roil ratio of 40%;
- S ⁇ E J306 defines the different viscosity grades of automotive gear lubricants.
- a m ⁇ ltigrade automotive gear lubricant refers to an automotive gear lubricant that has viscosity/temperature characteristics which fall within the limits of two different SAE numbers in SAE J3O6, June 1998.
- an SAE 75 W-90 automotive gear lubricant has a maximum temperature of -40°C for a viscosity of 150,000 cP and a kinematic viscosity at 100°C between 13.5 and less than 24.0 cSt.
- the second SAE viscosity grade, XX, for a muhigrade automotive gear lubricant is always a higher number than the proceeding "W" SAE viscosity grade; thus you may have an 80W-90 multigradc automotive gear lubricant but not an 80W-S0 niultigradc automotive scar lubricant.
- automotive gear lubricants are manna! transmission fluids, axle lubricants and differential fluids.
- the Maximum Temperature for Viscosity of ! 50,000 cP (°C) is measured by scanning Brookfield Viscosity by ⁇ STM D 2983-04.
- Gear lubricants having a low BrookikSd viscosity, especially those with a low Brookfield Ratio are especially desired.
- a low Brookfield Ratio is associated with improved low temperature properties of the gear lubricant.
- Brookfield Ratio Brookfield Viscosity in cP, measured at Temperature ⁇ in °C, divided by the Kinematic Viscosity at 100 ⁇ C in cSt. Temperature ⁇ ⁇ -4O°C when the gear lubricant is an SAE 75 W-XX.
- the Brookfleld Ratio of the gear lubricant of this invention is less than an amount calculated based on the Temperature ⁇ by the following equation:
- the Brookfield Ratio is less than 10081, preferably less than 8000; for an S ⁇ E 80W-XX automotive gear lubricant, the Brookfield Ratio is less than 3783.3, preferably less than 2500; and for an SAE 85W-XX automotive gear lubricant, the Brookfield Ratio is less than 1419,9.
- XX in this invention refers to the SAE viscosity grades of 80, 85, 90, 140, or 250.
- the XX for an automotive gear lubricant will always be a higher number than the proceeding "W" SAE viscosity grade; thus you may have an 80W-90 gear lubricant but not a 8OW-8O gear lubricant.
- gear lubricants of this invention are a preferred subset of those meeting the SAE J 306 specification.
- an SAE 75W-90 oil with a Brookfieid viscosity at the maximum of 150,000 cP divided by a typical kinematic viscosity at 100°C of 14 cSt would have a Brookfield Ratio of 10714, which would nol be as desired as the lubricants of this invention with a lower Brookfield Ratio.
- the gear lubricants of this invention have a higher kinematic viscosity at 100°C than oilier oils made from a waxy feed having low Broukfield viscosities.
- the gear lubricants of this invention have a kinematic viscosity at 1 QO 13 C greater than 10 cSt. Preferably they have a kinematic viscosity at 100°C less than or equal to 4 ! .0 cSt.
- the gear lubricants of this invention comprise greater than 12 wt°/o, more preferably greater than 15 wt%, most preferably greater than 25 wt% of a base oil having:
- Fischer-Tropsch derived or ' 1 FT derived means thai the product, fraction, 15 or feed originates from or is produced at some stage by a Fischer-Tropsch process.
- the feedstock for the Fischer-Tropsch process may come from a wide variety of hydrocarbonaceous resources, including natural gas, coal, shale oil, petroleum, municipal waste, derivatives of these, and combinations thereof,
- Waxy feed is a feed or stream comprising hydrocarbon molecules with a carbon number of C20+ and having a boiling point generally above about 600 0 F (316°C).
- the waxy feeds useful in the processes disclosed herein may be synthetic waxy feedstocks, such as Fischer-Tropsch waxy hydrocarbons, or may be derived from natural sources. Accordingly, the waxy feeds to the processes may comprise Fischer-Tropsch derived
- waxy feeds petroleum waxes, waxy distillate stocks such as gas oiis, lubricant oil stockS j high pour point polyalphaolefins, foots oils, normal alpha olefin waxes, slack waxes, deoiled waxes, and microcrystallme waxes, and mixtures thereof.
- the waxy feedstocks are derived from Fischer-Tropsch waxy feeds.
- Slack wax can be obtained from conventional petroleum derived feedstocks by either hydrocracki ⁇ g or by solvent refining of the lube oil fraction.
- slack wax is recovered from solvent dewaxing feedstocks prepared by one of these processes. Ilydrocracking is usual Iy preferred because hydrocracking will also reduce the nitrogen content to a low value. With slack wax derived from solvent refined oils, deoiiing may be used to reduce the nitrogen content. Hydrotreating of the slack wax can be used to lower the nitrogen and sulfur content.
- Slack waxes possess a very high viscosity index, normally in the range of from about 140 to 200, depending on the oil content and the starting material from which the slack wax was prepared. Therefore, slack waxes are suitable for the preparation of base oils having a very high viscosity index.
- the waxy feed useful in this invention preferably has iess than 25 ppm total combined nitrogen and sulfur.
- Nitrogen is measured by melting the waxy feed prior to oxidative combustion and cherai luminescence detection by ASTM D 4629-96, 'The test method is further described in U.S. Patent No. 6,503.956, incorporated herein.
- Sulfur is measured by melting the waxy feed prior to ultraviolet fluorescence by ASTM D 5453-00. The test method is further described in U.S. Patent No. 6,503,956, incorporated herein.
- Waxy feeds useful in this invention are expected to be plentiful and relatively cost competitive in the near future as large-scale Fischer- Tropsch synthesis processes come into production.
- Syncrude prepared from the Fischer-Tropsch process comprises a mixture of various solid, liquid, and gaseous hydrocarbons.
- Those Fischer-Tropsch products which boil within the range of lubricating base oil contain a high proportion of wax which makes them ideal candidates for processing into base oil. Accordingly, Fischer-Tropsch wax represents an excellent feed for preparing high quality base oiis according to the process of the invention
- Fischer-Tropsch wax is normally solid at room temperature and, consequently, displays poor low temperature properties, such as pour point and cloud point.
- Fischer-Tropsch derived base oils having excellent low temperature properties may be prepared.
- a general description of suitable hydroisomerizatio ⁇ dewaxlng processes may be found in U.S. Patent Nos. 5,135,638 and 5 ,282,958 ; and U.S. Patent Application Publication No. 20050133409, incorporated herein.
- the hydro isomerization is achieved by contacting the waxy feed with a hydroisomerization catalyst in an isora ⁇ izat ⁇ on zone under hydroisomerizing conditions.
- the hydroisomerization catalyst preferably comprises a shape selective intermediate pore size molecular sieve, a noble metal hydrogcnation component, and a refractory oxide support.
- the shape selective intermediate pore size molecular sieve is preferably selected from the group consisting of SAPO-1 1 , SAPO-31 , SAPO-41 , SM-3, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-S7, SSZ-32, offretite, ferrieriie, and combinations thereof, SAPO-1 1, SM-3, SSZ-32, ZSM-23, and combinations thereof are more preferred.
- the noble metal hydrogenatio ⁇ component is platinum, palladium, or combinations therco F.
- hydroisomeriz ⁇ ng conditions depend on the waxy feed used, the hydroisomerization catalyst used, whether or not the catalyst is suifided, the desired yield, and the desired properties of the base oil.
- Preferred hydroisomerizing conditions useful in the current invention include temperatures Of ZoO°C to about 413°C (500 to about 775T), a total pressure of 15 to 3000 psig, and a hydrogen to feed ratio from about 0.5 to 30 MSCF/bbl, preferably from about 1 to about 10 MSCF/bbl, more preferably from about 4 to about 8 MSCF/bbl.
- hydrogen will be separated from the product and recycled to the isomerization zone.
- the base oil produced by hydroisomerization dewaxing may be hydiofmished,
- the hydrofinishing may occur in one or more steps, either before or after fractionating of the base oil into one or more fractions.
- the hydrofinishing is intended to improve the oxidation stability, UV stability, and appearance of the product by removing aromatics, olefins, color bodies, and solvents, A general description of hydrofinishing may be found in U.S. Patent Nos. 3,852,207 and 4,673,487, incorporated herein.
- the hydrofinishing step may be needed to reduce, the weight percent olefins in the base oi! to less than 10, preferably less than S, more preferably less than I 5 and most preferably less than 0.5.
- the Isydroil ⁇ ishing step may also be needed to reduce the weight percent aromatics to less than 0.1 , preferably less than 0.06. more preferably less than 0.02, and most, preferably less than 0.01 .
- the base oil is fractionated into different viscosity grades of base oil.
- “different viscosity grades of base oil” is defined as two or more base oils differing in kinematic viscosity at 100°C from each other by at least 1 .0 cSi. Kinematic viscosity is measured using ASTM D 445-04. Fiaction ⁇ ting is done using a vacuum distillation unit to yield cuts with pre-selecicd boiiing ranges.
- the base oil fractions will typically have a pour point less than 0 ⁇ J C. Preferably, the pour point will be less than -10°C. Additionally, in some embodiments the pour point of the base oil fraction will have a ratio of pour point, in °C, to the kinematic viscosity at 100°C, in cSL greater than a Base Oil Pour Factor, where the Base Oil Pour Factor is defined by the equation:
- Base Oil Pour Factor 7,35 x Ln(Ki n ⁇ rnatie Viscosity at I UO°C) -18
- the base oil fractions have measurable quantities of unsaturated molecules measured by FIMS.
- the h ⁇ droisomerization dcwaxing and fractionating conditions in the process of this invention are tailoied to produce one or more selected tractions of base oH Ha ⁇ ing greater than 10 ⁇ vt% total molecules with cycloparaffinic functionality, preferably greater than 20. greater than 35, or greater than 40: and a viscosity index gteater than 150.
- the one or more selected fractions of base oils will usually have less than 70 wt% total molecules with cycloparaffinic functionality.
- the one or more selected fractions of base oil will additionally have a ratio of molecules with monocycloparaffinic functionality to molecules with muUicycloparaffmic functionality greater than 2.1.
- die base oil has a ratio of molecules with monocycloparaffinic functionality to molecules with multicyeloparaff ⁇ nic functionality greater than 5, or greater than 12.
- the base oil may contain no molecules, with multicycloparaffinic functionality, such that the ratio of molecules with monocycloparaffinic functionality to molecules with mul ⁇ cycioparaffinie functionality is greater than 100,
- the lubricant base oil fractions useful in this ⁇ we ⁇ tiun have a viscosity index greater than an amount defined fay the equation:
- V] 28 x LnCKinemaiie Viscosity at 100°C) ⁇ 95
- lubricant base oil fractions useful in this invention have a viscosity index greater than an amount defined by the equation:
- the base oil fractions have a weight percent olefins less than 10. preferably less than 5, more preferably iess than L and most preferably less than 0.5,
- the base oil fractions preferably have a weight percent arornatics iess than 0.1, more preferably less than 0.05, and most preferably less than 0.02,
- the base oil fractions have a traction coefficient iess than 0.023, preferably less than or equal to 0.021, move preferably less than or equal to 0.019, when measured a ⁇ a kinematic viscosity of 15 cSt and at a slide to roll ratio of 40%.
- they Preferably, they have a traction coefficient less than an amount defined by the equation:
- the base oil fractions having a low traction coefficient also have large film thicknesses. That is they have an EHD film thickness greater than 175 nanometers when measured at a kinematic viscosity of 15 cSt.
- the preferred base oils of this invention have film thicknesses about the same or thicker than PAOs, but have lower traction coefficients than PAOs.
- the base oil fractions have a traction coefficient less than 0.017, or even less than 0.015, or less than 0.01 1 , when measured at 15 cSt and at a .slide to roll ratio of 40%.
- the base oil fractions having the lowest traction coefficients have unique branching properties by NMR, including a branching index less than or equal to 23.4, a branching proximity greater than or equal to 22,0, and a Free Carbon Index between 9 and 30. Additionally they preferably have greater than 4 wt% naphthenic carbon, more preferably greater than 5 wt% naphthenic carbon by ndM analysis by ASTM D 3238.
- the base oil fractions having the lowest traction coefficients generally have a pour point less than -15°C, but surprisingly may have a ratio of pour point, in °C, to the kinematic viscosity at 100°C, in eSt, less than an amount defined by the equation:
- the base oil fractions having the lowest traction coefficients have a higher kinematic viscosity and higher boiling points.
- the lubricant base oil fractions having a traction coefficient less than 0.015 have a 50 vvt% boiling point greater than 1032°C (1050 D F)
- the lubricant base oil fraction of the invention has a traction coefficient less thai 0.01 1 and a 50 ⁇ vt% boiling point by ASTM D 6353 greater than 582°C (1 OSO 13 F).
- the lubricant base oil fractions useful in this invention unlike polyalph&olefins (PAO?) and many other synthetic lubricating base oils, contain hydrocarbon molecules having consecutive numbers of carbon atoms. This is readily determined by gas chromatography, where the lubricant base oil fractions boil over a broad boiling range and do not have sharp peaks separated by more than 1 carbon number. In other words, the lubricating base oil fractions have chromatographic peaks at each carbon number across their boiling range.
- the Qxidat ⁇ r BN of the lubricant base oil fraction most useful in the invention is greater than 10 hours, preferably greater than 12 hours, In preferred embodiments, where the olefin and aromatics contents are significantly low in the lubricant base oil fraction of the lubricating oil, the Oxidator BN of the selected base oil fraction will be greater than 25 hours, preferably greater than 35 hours, more preferably greater than 40 or even 41 hours. The Oxidator BN of the selected base oil fraction will typically be less than 60 hours. Oxidator BN is a convenient way to measure the oxidation stability of base oils. The Oxidator BN test is described by Stangeiand et a!, in U.S. Patent No. 3,852,207.
- the Oxidator BN test measures the resistance to oxidation by means of a Dornte-type oxygen absorption apparatus. See R.W. Domte "Oxidation of White Oils," Industrial and Engineering Chemistry, Vol. 28, page 26, 1936, Normally, the conditions are one atmosphere of pure oxygen at 34O 0 F, The results arc reported in hours to absorb 1000 nil of 02 by 100 g. of oil.
- 0.8 ml of catalyst is used per 100 grams of oil and an additive package is included in the oil.
- the catalyst is a mixture of soluble metal naphthenates in kerosene. The mixture of soluble metal naphthenates simulates the average metal analysis of used crankcase oil.
- the level of metals in the catalyst is as follows:
- the additive package is 80 mil ⁇ moles of zinc bispolypropylesiephenySdithio-phosphate per 100 grams of oil, or approximately 1 .1 grams of OLOA 260.
- the Oxidalor BN test measures the response of a lubricating base oi) in a simulated application. High values, or long limes to absorb one liter of oxygen, indicate good oxidation stability,
- OLOA is an acronym for Oronite Lubricating Oil Additive®, which is a registered trademark of Chevron Oronite.
- the finished lubricant of the present invention comprises an effective amount of one or more lubricant additives.
- Lubricant additives which may be blended with the lubricating base oil to form the finished lubricant composition include those which are intended to improve certain properties of the finished lubricant.
- Typical lubricant additives include, for example, anti-wear additives, EP agents, detergents, dispersants, antioxidants, pour point depressants, Viscosity Index improvers, viscosity modifiers, friction modifiers, demuisifiers, antilbaming agents, corrosion inhibitors, rust inhibitors, seal swell agents, emulsifiers, wetting agents, lubricity improvers, metal deactivators, gelling agents, tackiness agents, bactericides, fluid-loss additives, colorants, and the like.
- the total amount of one or more lubricant additives in the finished lubricant is within the range of 0.1 to 30 wt%.
- the amount of lubricating base oil of this invention in the finished lubricant is between IO and 99,9 wt%, preferably between 25 and 99 wt%.
- Lubricant additive suppliers will provide information on effective amounts of their individual lubricant additives or additive packages to be blended with lubricating base oils to make finished lubricants.
- less additives than required with lubricating base oils made by other processes may be required to meet the specifications for the finished lubricant.
- Viscosity Index Improvers Vl Improvers
- VI improvers modify the viseometric characteristics of lubricants by reducing the rate of thinning with increasing temperature and the rate of thickening with low temperatures. VI improvers thereby provide enhanced performance at low and high temperatures, Vl improvers are typically subjected to mechanical degradation due to shearing of the molecules in high stress areas. High pressures generated in hydraulic systems subject fluids to shear rates up to l ⁇ 's '! . Hydraulic shear causes fluid temperature to rise in a hydraulic system and shear may bring about permanent viscositv loss in lubricatin *ge oils.
- VJ improvers are oil soluble organic polymers, typically olefin homo- or co-polymers or derivatives thereof, of number average molecular weight of about 15000 to 1 million atomic mass units (amu).
- Vl improvers are generally added to lubricating oils at concentrations from about 0.1 to 10 wt%. They function by thickening the lubricating oil to which they are added more at high temperatures than Sow, thus keeping the viscosity' change of the lubricant with temperature more constant than would otherwise be the case.
- the change in viscosity with temperature is commonly represented by the viscosity index (VI), with the viscosity of oils with large VI (e.g., 140) changing less with temperature than the viscosity of oils with low Vl (e.g., 90),
- Vl improvers include: polymers and copolymers of methacrylate and acrylate esters; ethylene-propylene copolymers; styrene-diene copolymers; and polyisobutylene, Vl improvers are often hydrogenaied to remove residua! olefin.
- Vl improver derivatives include dispersant VI improver, which contain polar functionalities such as grafted succinimide groups.
- the gear lubricant of the invention has less than 10 wt% VI improver, preferably less than 5 wt% VI improver.
- the gear lubricant may contain very low levels of Vl improver, such as less than 2 wt% or less than 0.5 wt%, preferably less than 0,4 more preferably less than 0.2 wt% of Vl improver.
- the gear lubricant may even contain no VI improver.
- Thickeners in the context of this disclosure are oil soluble or oil miscible hydrocarbons with a kinematic viscosity at 100°C greater than iOO cSt.
- thickeners are polyisobutyiene. high molecular weight complex ester, butyl rubber, olefin copolymers, styrene-diene polymer, poiymethacrylate, styrene-ester, and ultra. high viscosity PAO.
- the thickener has a kinematic viscosity at 100°C of about ] 50 cSt to about 10,000 cSt.
- ihe gear lubricant of the invention has less than 2 wt% thickener
- distillate fraction or “distillate” refers to a side stream fraction recovered either from an atmospheric fractionation column or from a vacuum column as opposed to the "bottoms” which represents the residual higher boiling fraction recovered from the bottom of the column.
- Atmospheric distillation is typically used to separate the lighter distillate fractions, such as naphtha and middle distillates, from a bottoms fraction having an initial boiling point above about 600T to about 75O 0 P (about 315 0 C to about 399°C).
- Vacuum distillation is typically used to separate the higher boiling material, such as the lubricating base oil fractions, into different boiling range cuts. Fractionating the lubricating base oil into different boiling range cuts enables the lubricating base oil manufacturing plant to produce more than one grade, or viscosity, of lubricating base oil.
- the gear lubricants of the present invention further comprise at least one pour point depressant They contain from about 0.01 to 12 wt% based upon the total lubricant blend of a pour point depressant.
- Pour point depressants are known in the art and include, but are not limited to esters of maletc anhydride-styrene copolymers, polymeihacrylates.
- the pour point depressant is polymethacrylate.
- the pour point depressant utilized in the present invention may also be a pour point depressing base oil blending component prepared from an isomerized
- the pour point depressing base oil blending component reduces the pour point of the lubricant blend at least 3°C below the pour point of the lubricant blend in the absence of the pour point depressing base oil blending component.
- the pour point depressing base oil blending component is an isomerized Fischer-Tropseh derived bottoms product having a pour point that is at least 3°C higher than the pour point of the lubricant blend comprising the lubricant base oil fraction derived from highly paraffinic wax and the petroleum derived base oil (i.e., the blend in the absence of a pour point depressant).
- the target pour point of the lubricant blend is -9°C and the pour point of the lubricant blend in the absence of pour point depressant is greater than -9°C, an amouni ⁇ f the pour point depressing base oil blending component of the invention will be blended with the lubricant blend in sufficient proportion to lower the pour point of the blend to the target value.
- the isomerized Fischer-Tropsch derived bottoms product used to lower the pour point of the lubricant blend is usually recovered as the bottoms from the vacuum column of a Fischer-Tropsch operation.
- the average molecular weight of the pour point depressing base oil blending component usually will fail within the range of from about 600 to about 1 100 with an average molecular weight between about 700 and about 1000 being preferred.
- the pour point of the pour point depressing base oil blending component will be between about -9°C and about 20°C.
- the 10% point of the boiling range of the pour point depressing base oil blending component usually will be within the range of from about 850 0 F and about 1050 0 F, Preferably, the pour point depressing base oil blending component will have an average degree of branching in the molecules between about 6.5 and about 10 alkyl branches per H ) O carbon atoms.
- the lubricant blend may comprise a pour point depressant well known in the art and a pour point depressing base oil blending component.
- the pour point depressing base oil blending component may be an. isomerized
- the lubricant blend comprises 0.05 to 15 wt% (more preferably 0.5 to 10 wt%) pour point depressing base oil blending component that is isomerized Fischer-Tropsch derived, or petroleum derived, bottoms product.
- Bright stock is a high viscosity base oil which is named for the SUS viscosity at 21O 0 F.
- Petroleum derived bright stock will have a viscosity above
- Bright stock derived from Daqing crude has been found to be especially suitable for use as the pour point depressing base oil blending component of the present invention
- the bright stock should be hydroisomerized and may optionally be solvent dewaxed.
- Bright stock prepared solely by solvent dcwaxmg has been found to be much less effective as a pour point depressing base oil blending component.
- the gear lubricants of this invention comprise between 2 and 35 V 1 I 0 Zo 1 preferably between 2.5 and 30 wt%, more preferably between 2.5 and 20 wt%, of an extreme pressure (EP) gear lubricant additive.
- EP gear lubricant additives are added to lubricants to prevent destructive metal-to-metal contact in the lubrication of moving surfaces. While under norma! conditions termed “hydrodynatnie", a film of lubricant is maintained between the relatively moving surfaces governed by lubricant parameters, and principally viscosity.
- EP gear lubricant additives have been oil soluble or easily dispersed as a stable dispersion in the oil, and largely have been organic compounds chemically reacted to contain sulfur, halogen (principally chlorine), phosphorous, earboxyl, or earboxylate salt groups which react with the metal surface under boundary lubrication conditions.
- Stable dispersions of hydra ted alkali metal borates have also been found to be effective as EP gear lubricant additives.
- hydrated alkali metal borates are insoluble in lubricant oil media, it is necessary to incorporate the borate as a dispersion in the oil and homogenous dispersions are particularly desirable.
- the degree of formation of a homogenous dispersion can be correlated to the turbidity of the. oil after addition of the hydrated v - alkali metal borate with higher turbidity correlating to less homogenous dispersions. in order to facilitate formation of such a homogenous dispersion, it is conventional to include a d ⁇ spersa ⁇ l in such compositions.
- dispersants include lipophilic surface-active agents such as alkcnyl succinimides or other nitrogen containing dispersants as well as alkenyl succinates.
- a preferred EP gear lubricant additive of this invention comprises an oil dispersion of hexagonal boron nitride,
- Other preferred EP gear lubricant additives of this invention comprise a dispersed hydrated potassium borate or dispersed hydrated sodium borate composition having a specific degree of dehydration.
- the dispersed hydrated potassium borate compositions arc described in U.S. Patent No. 6,737,387.
- the dispersed hydrated potassium borate is characterized by a hydroxy!: boron ratio (OH:B) of from at least 1.2: 1 to 2.2; 1 , and a potassium to boron ratio of from about 1:2.75 to 1 :3.25.
- the dispersed hydrated sodium borate compositions arc described in U.S. Patent No. 6,634,450.
- the dispersed hydrated sodium borate is characterized by a hydroxy!: boron ratio (OH:B) of from about 0.80: 5 to 1.60: 1 , and a sodium to boron ratio of from about 1 :2.75 to 1 :3.25,
- the preferred EP gear lubricant additive of this invention comprises a combination of three components, which are (1) hydrated alkali metal borates; (2) at least one dihydrocarbyl polysisltlde component comprising a mixture including no more than 70 wt.% dihydrocarbyl trisulfide, more than 5.5 wt.% dihydrocarbyl disulfide, and at least 30 wt.% dihydrocarbyl tetrasulfide or higher polys ⁇ lftdes; and (3) a non-acidic phosphorus component comprising a trihydroearbyi phosphite component, at least 90 wt.% of which has the formula (RO) 3 P 1 where R is alkyl of 4 to 24 carbon atoms and at least one dihydrocarbyl dithiophosphale derivative.
- R is alkyl of 4 to 24 carbon atoms and at least one dihydrocarbyl dithiophosphale derivative.
- the KP gear lubricant additive is typical!) combined with other additives in a gear 5 lubricant additive package
- oiher additives can be ptesent in the geai lubricants of the present invention. These additives include antioxidants, viscosity Index improvers, dispeisants, rust inhibitors, foam inhibitors, corrosion inhibitois, other a ⁇ tittear agents, demuisitlers, friction modifiers, pour point depressants and a variety of other well-known additives
- Preferred dispersants include the well known l( ⁇ sucemimide and cthoxylated alkylphenoh and alcohoU.
- Particularly preferred additional additives are the oil-soluble suecimmides and oil-soluble alkali or alkaline earth metal sulfonates.
- the gear lubricant of this invention may aba comprise other base oils, such as for
- Group I 1 Group U 5 petroleum derived Group 111 or synthetic base oils such as polyalphaolefi ⁇ s, esieis, polyglycols, poiyisobutenes, and alkylated naphthalenes.
- Some embodiments of the gear lubricants of this invention comprise a pour pomt depressing base oil blending component.
- the pour point depressing base oil blending component is usually prepared from the high boiling bottoms fraction remaining in the vacuum tower after distilling OiT the lower boiling base
- raoleculai weight of at least 600 It may be prepared from either a Fiseher-l ropsch deiived bottoms or a petroleum derhed bottoms, l he bottoms us hydroisomerized to achieve an average decree of branching in the molecule between about 5 and about 9 aikyi-branches per 100 caibon atoms. Following hydroisomerization the pour pomt depressing base oil blending component
- the pour point depressing base oil blending component is prepared from the waxy fraction that is normally a solid at room temperature.
- the waxy fraction may be produced directly from the Fischer-Tropsch syncmde or it may be. prepared from the oligomerixatiori of lower boiling
- Fischer-Tropsch derived olefins Regardless of the source of the Fischer-Tropsch wax, it must contain hydrocarbons boiling above about 950 0 F in order to produce the bottoms used in preparing the pour point depressing base oil blending component, In order to improve the pour point and VL the wax is hydroisomerized to introduce favorable branching into the. molecules.
- the bydroisornerized wax will usually be sent to a vacuum column where the various distillate base oil cuts are collected.
- these distillate base oil fractions may be used for the hydroisomcrized Fischer-Tropsch distillate base oil.
- the bottoms material collected from the vacuum column comprises a mixture of high boiling hydrocarbons which are used to prepare the pour depressing base oil blending component.
- the waxy fraction may undergo various other operations, such as, for example, hydrocracking, hydrotreating, and hydro finishing.
- the pour point depressing base, oil blending component of the present invention is not an additive in the normal use of this term within the art, since it is really only a high boiling base oil fraction.
- the pour point depressing base oil blending component will have a pour point that is at least 3°C higher than the pour point of the hydroisomerized Fischer-Tropsch distillate base oil. It has been found that when the hydroisomerized bottoms as described in this disclosure is used TO reduce the pour point of the blend, the pour point of the blend will be below the pour point of both the pour point depressing base oil blending component and the nydroisomerized distillate Fischer-Tropsch base oil. Therefore, it is not necessary to reduce the pour point of the bottoms to the target pour point of the engine oil.
- the actual degree of hydroisomerization need not be as high as might, otherwise be expected; and the hydroisomerization reactor may be operated at lower severity with less cracking and less yield loss. It has been found that the bottoms should not be over hydroisomerized or its ability to act as a pour point depressing base o ⁇ ! blending component will be compromised, Accordingly, the average degree of branching in the molecules of the Pischer-Tropsch bottoms should fail within the range of from about 5 to about 9 alky] branches per 100 carbon atoms.
- a pour point depressing base oil blending component derived from a Fischer-Tropsch feedstock will have an average molecular weight between about 600 and about 1,100, preferably between about 700 and about 1 ,000.
- the kinematic viscosity at 100°C will usually fall within the range of from about 8 cSt to about 22 cSt. I he 10% boiling point of the boiling range of the bottoms typically will fall between about 85O 0 F and about 1050 0 F.
- the higher molecular weight hydrocarbons are more effective as pour point depressing base oil blending components than the lower molecular weight hydrocarbons.
- the molecular weight of the pour point depressing base oil blending component will be 600 or greater. Consequently, higher cut points in the fractionation column which result in a higher boiling bottoms material are usually preferred when preparing the pour point depressing base oil blending component.
- the higher cut point also has the advantage of producing a higher yield of the distillate base oil fractions.
- Blight stock constitutes a bottoms ft action which has been highly iefined and de ⁇ va ⁇ ed.
- Blight stock is a high viscosity base nil which is named for the SUS viscosity at 2!O 0 F.
- Typical! ⁇ petroleum derived bright stock wtH have a viscosity above i SO cSt at 40°C, preferably above 250 eSt at 40 13 C, and more preferably mngmg
- Bright stock de ⁇ ed from Daqirg crude has been found to be especially suitable for use as the pour poml depressing base oil blending component of the present invention
- the bright stock should be hydioisomerizcd and may optionally be solvent dewaxed B ⁇ ght stock prepared solely by solvent denaxmg has been found to be much less effective as a pour point depressing base oil blending U component
- the petroleum derived poui point depressing base oil blending component preferably will have a paraffin content of at least about 30 wt%, moie preferably ai least 40 ⁇ vt%, and most preferably at least 50 ⁇ t%.
- the boiling range of the 5 pour point depressing base oil blending component should be above about 950 0 F (51 O°C)
- the 10% boiling point should be greater than about IQ5O U F (565X) with a 10% point in excess of 1 150"F (62O°C) being lecturrred
- the avemgc degree of branching in the molecules of the petroleum derived poui point depressing base oil blending component preferably will fall within the range oi 0 from about 5 to about 9 alkyi-branchcs per 100 carbon atoms, mote strategicallyrably from about 6 tu about S alkyl-branches per 100 carbon atoms.
- the Wt% Olefins in the base oils of this invention is determined by proton-NMR by the following steps, A-D;
- the instrument When a 30° pulse is applied, the instrument must have a minimum signal digitization dynamic range of 65.000. Preferably the dynamic range will be 260,000 or more.
- wl% olefins by proton NM R 100 times the number of double bonds times the number of hydrogens in a typical olefin molecule divided by the number of hydrogens in a typical test substance molecule.
- the wt% olefins by proton NMR calculation procedure, D. works best when the percent olefins result is low, less than about 15 wt%.
- the olefins must be "conventional" olefins; i.e. a distributed mixture ofthose olefin types having hydrogens attached to the double bond carbons such as: aipha, vinylidene, cis, trans, and tri substituted. These olefin types will have a detectable allylic to olefin integral ratio between 1 and about 2.5. When this ratio exceeds about 3, it indicates a higher percentage of tri or tetra substituted olefins are present and that different assumptions must be made to calculate the number of double bonds in the sample.
- the method used to measure low levels of molecules with at least one aromatic function hi the lubricant base oils of this invention uses a
- Identification of the individual aromatic classes in the highly saturated Base oils was made on the basis of their UV spectral pattern and their elution time.
- the amino column used for this analysis differentiates aromatic molecules largely on the basis of their ring- number (or more correctly. double-bond number).
- the single ring aromatic containing molecules clute first, followed by the polycycUe aromatics in order of increasing double bond number per molecule.
- those with only alkyl substitution on the ring elute sooner than those with naphthenic substitution.
- Quantitation of the eluting aromatic compounds was made by integrating chromatograms made from wavelengths optimized for each general class of compounds over the appropriate retention time window for that aromatic.
- Retention time window limits for each aromatic class wcie determined by manually evaluating (he individual absorbance spectra of eluting compounds at different times and assigning them to the appropriate aromatic class based on their qualitative similarity to model compound absorption spectra. With few exceptions, only Five classes of aromatic compounds were observed in highly saturated API Group H and III lubricant base oils.
- MPLC-UV is used for identifying these classes of aromatic compounds even at very- low levels.
- Multi-ring aromatics typically absorb 10 to 200 times more strongly than single-ring aromatics.
- Alkyl-s ⁇ bstitution also affected absorption by about 20%. Therefore, it is important to use HPLC to separate and identify the various species of aromatics and know how efficiently they absorb.
- alkyi-cyclohexylbenzene molecules in base oils exhibit a distinct peak absorbance at 272nm that corresponds to the same (forbidden) transition that ynsubst ⁇ tuted tetralin model compounds do at 268nm
- concentration of alkyl-1 -ring aromatic naphthenes in base oil samples was calculated by assuming that its moiar absorptivity response factor at 272nm was approximately equal to tetralin's molar absorptivity at 268nm, calculated from Beer's law plots. Weight percent concentrations of aromatics were calculated by assuming that the average molecular weight for each aromatic class was approximately equa ⁇ to ⁇ he average molecular weight for the whole base oil sample.
- This calibration method was further improved by isolating the 1 -ring aromatics directly from the lubricant base oils via exhaustive ⁇ IPLC chromatography
- the substituted benzene aiomatics were separated from the bulk of the lubricant base oil using a Waters semi-preparative HPLC unit 10 grams of sample was diluted 1 : 1 in n-hexane and injected onto an arnino-bouded silica column, a 5cm x 22,4mm ID guard. followed by two 25cm x 22 4mm ID columns of 8-12 micron amino-bo ⁇ ded silica particles, manufactured by Rairrin Instruments, Emeryville, California, with ⁇ -hexat ⁇ e as the mobile phase at a flow rate of 18m!s/ ' min.
- NMR NMR was easier to calibrate than HPLC UV because it simply measured aromatic carbon so the response did not depend on the class of aromaiics being analysed.
- the NMR results weie translated from % aromatic carbon to % aromatic molecules (to be consistent with HPLC-UV and ⁇ 2007) by knowing that 95-99% of the aromaties in highly saturated lubricant base oils were smgle- ⁇ ng aiomaties.
- the lubricant base oils of this invention were characterized by Field Ionization Mass Spectroscopy (FJMS) into alkanes and molecules with different numbers of unsaturations. The distribution of the molecules in the oil fractions was determined by FlMS.
- the samples were introduced via solid probe, preferably by placing a small amount (about 0.1 mg,) of the base oil to be tested in a glass capillary tube.
- the capillary tube was placed at the tip of a solids probe for a mass spectrometer, and the probe was heated from about 40 to 50°C up to 500 or 600°C at a rate between 5Q*C and K)O°C per minute in a mass spectrometer operating at about 10 ' " torr.
- the mass spectrometer was scanned from m/z 40 to m/z 1000 at a rate of 5 seconds per decade.
- the mass spectrometer used was a Micromass Time-oi-Flighl. Response factors for all compound types were assumed to bs 3 ,0, such that weight percent was determined from area percent. The acquired mass spectra were summed to generate one "averaged" spectrum.
- the lubricant base oils of this invention were characterized by FIMS into alkaries and molecules with different numbers of unsaturations.
- the molecules with different numbers of unsaturations may be comprised of cycloparaffins, olefins, and aromatics. If aromaties were present in significant amounts in the lubricant base oil they would be identified in the FiMS analysis as 4- unsaturate ⁇ ns. When olefins were present in significant amounts in the lubricant base oil they would be identified in the FIMS analysis as 1 -unsaturations.
- the total of the 1 -imsaturaiions, 2-unsalurations, 3 -unsaturations, 4-unsatiirations, 5 -unsaturations, and 6-unsaturations from the FIMS analysis, minus the wt% olefins by proton NM(I, and minus the wt% aromatics by HPLC-UV is the total weight percent of molecules with eyeloparaffinic functionality in the lubricant base oils of this invention. Note that if the aromalics content was not measured, it was assumed to be less than 0.1 wt% and not included in the calculation for total weight percent of molecules with cycloparaffmic functionality.
- Molecules with cycloparaffmic functionality mean any molecule that is, or contains as one or more substiuients, a monocyclic or a fused multicyclic saturated hydrocarbon group.
- the cycloparaffmic group may be optionally substituted with one or more substituents.
- Representative examples include, but are not limited to. cyclopropyi, cyclobutyl, cyclopentyl, cyclohexyl, cyclohepiyl, decahydronaphthalene, octahydropentalene, (pentadeca ⁇ - ⁇ -yOcyclohexane, 3,7, 10-t ⁇ cyclohexy ipentadecane. decahydro-l -(pentadecan-6-yl)naphthalene, and the like.
- Molecules with mon ⁇ cycloparaffmic functionality mean any molecule that Ls a monocyclic saturated hydrocarbon group of 3 to 7 ring carbons or any molecule that is substituted with a single monocyclic saturated hydrocarbon group of 3 to 7 ring carbons.
- the cycioparaffmic group may be optionally substituted with one or more substituents.
- Representative examples include, but arc .not limited to, cyeiopropyi, cyciobutyl, cyclopentyl, cyclohexyl, eyeiohepty ⁇ , (penladeca ⁇ -6-yl) cyelohexanc, and the like.
- Molecules with mukicycloparaff ⁇ nic functionality mean any molecule that is a fused multicyclic saturated hydrocarbon ring group of two or more fused rings, any molecule that is substituted with one or more fused multicyclic saturated hydrocarbon ring groups of two or more fused rings, or any molecule that is substituted with more than one monocyclic saturated hydrocarbon group of 3 to 7 ring carbons.
- the fused multicyclic saturated hydrocarbon ring group preferably is of two fused rings.
- the cycloparaffinic group may be optionally substituted with one or more substituents. Representative examples include, but are not limited to.
- the branching properties of the base oils of the present invention was determined by analyzing a sample of oil using carbon- 13 ( ! 3 C) NMR according to the following ten-step process. References cited in the description of the process provide details of the process steps. Steps 1 and 2 are performed only on the initial materials from a new process.
- the number of branches per molecule is the sum of the branches found in step 4.
- T he number ol alk>l branches per 100 carbon atoms is calculated from the number of bianches per molecule (step 6 ⁇ times lO Q /a ⁇ eiage carbon number.
- FCI Free Carbon Index
- step b divide the total carbon- 13 integral area (chart divisions or area counts) by the average carbon number from step a, to obtain the integral area per carbon in the sample,
- Measurements can be perlormed iising any Fourier Transform NMR spectrometer.
- the measurements are performed using a spectrometer having a magnet of 7.0 T or greater.
- the spectra! width for the !j CNMR studies was limited to the saturated carbon region, about 0-80 ppm vs. TMS (tetramethylsilanc). Solutions of 25-50% by weight in chloroform-d 1 were excited by 30° pulses followed by a 1.3secondacquisi ⁇ ion time.
- the broadband proton inverse-gated decoupling was used during a ⁇ seconddelay prior to the excitation pulse and on during acquisition.
- Samples were also doped with 0.0 " * to 0.05 M Cr(acac) 3 (iris (acetylacetonato)-chromium(ni)) as a relaxation agent to ensure lull intensities are observed.
- Total experiment times ranged from 4 to S hours
- the 1 H NMR analysis were also carried out using a spectrometer having a magnet uf 7,0 T or greater. Free induction decay of 64 coaveraged transients were acquired, employing a 90° excitation pulse, a relaxation decay of 4 seconds, and acquisition time of 1.2 seconds.
- DEPT Distortionless Enhancement by Polarization Transfer.
- the DEPT 45 sequence gives a signal all carbons bonded to protons.
- DEPT 90 shows CH carbons only.
- DEPT 135 shows CH and CII 3 up and CH 2 180° out of phase (down),
- APT is Attached Proton Test. It allows ail carbons to be seen, but if CH and CH ⁇ arc up, then quaternaries and CHj are down.
- the sequences are useful in that every branch methyl should have a corresponding CH. And the methyl group are clearly identified by chemical shift and phase. Both are described in the references cited.
- the blanching properties of each sample were determined by " C NMR using the assumption in the calculations that the entire sample was iso-paraffinic. Corrections were not made for n-paraff ⁇ ns or naphlhenes, which ma; 1 have been present in the oil samples in varying amounts, The naphthenes content may be measured using Field Ionization Mass Spectroscopy (FfMS).
- FfMS Field Ionization Mass Spectroscopy
- Alky means a linear saturated monovalent hydrocarbon radical of
- alky! branches are methyl
- alky! branches include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-hutyl, isobuiyi, sec-butyl, i-butyi, n-pentyl, and the like.
- a hydrotreated cobalt based Fischer-Tropsch wax had the following properties:
- a base oil, FT-7.3, was made from the hydrotreated cobalt based Fischer-Tropsch wax by hydroisoraerization dewaxing, hydrofinishing, fractionating, and blending to a viscosity target.
- the base oil had the properties as shown in Table 11.
- gear lubricant EP antiwear additive packages comprised sulfur phosphorus (SfP) and a stable dispersion of hydrated alkali metal borate EP additives, combined with other additives.
- SfP sulfur phosphorus
- the additives used in GEARA and GEARB were the same as those used in commercial production of Chevron Delo® (kar Lubricants ESI®.
- the additives used in GEARC were the same as those used in commercial production of Chevron Delo® Trans Fluid ESi®. Delo® and ESI® are registered trademarks of Chevron Corporation.
- the formulations of these three gear lubricant blends are summarized in Table 111.
- Citgo Bright Stock 150 is a petroleum derived Group 1 bright stock produced by solvent dewaxing.
- GEARA and GEARB are excellent gear lubricants for all types of automotive and industrial bearings and gears. They are suitable for top-off of limited slip differentials. They meet the requirements for the 750.000-mile extended warranty program in Dana/Spicer axles. GEARA also meets the requirements for extended service in Meritor axles for 500,000 mile oil drains. GEARC is ideally suited for heavy duty manual transmissions. GEARC meets the requirements for Eaton's 750,000-miJe extended warranty program for transmission fluids.
- GEARA, GEARB, and GEARC are examples of the gear lubricants of this invention with very !ow Brookfield viscosities relative to their kinematic viscosities. All three of them have a Brookfield Ratio (ratio of Brookfield Viscosity at ⁇ , in D C, divided by the kinematic viscosity at 100°C) less than or equal to an amount defined by the equation:
- GEARA and GEARC both had more than 12 wl% of the base oil, based on the weight of the total gear lubricant, having the more desired properties ⁇ f:
- Cilgo Bright Stock 150 is a Group ⁇ base oil having greater than 25 wt% aromatics and a Vl less than 100.
- FT-4.1 FT-4.3, FT-7.9, FT-8.0 and FT-16 were made from the same FT wax described in Example 1 , The processes used to make the base oils were hydroisomerization dewaxmg, hydrofmishing, fractionating, and blending to a viscosity target.
- FT- 16 was a vacuum distillation bottoms product. Hydrofinishing was done to a greater extent with these base oils, such that the olefins were effectively eliminated.
- a sixth base oil, FT-24 was made from a hydrotrcated Co-based FT wax having less than 0.2 ppm nitrogen, less than 6 ppm sulfur and a wt% of n-paraffm by GC of 76.01.
- the FI -24 base oil was made by hydroisomerization dewaxing, hydrofinishing. fractionating, and selection of a heavy bottoms product having a kinematic viscosity at 100°C greater than 20 cSt and a TIO boiling p ⁇ int greater than 1000 0 F.
- the six different base oils had the properties as shown in ' fable VII
- F ⁇ -4.1 , FT-4.3, FT-16, and FT-24 arc base oils having:
- FT-7.9 and FT-8 although having high Vl and total weight percent molecules with cycioparaffinic functionality, did not have a ratio of molecules with monocycloparalTi ⁇ ie functionality to molecules with muUicycloparaffinic functionality greater than 12.
- Fl ' - 16 and FT-24 are also pour point depressing base oil blending components prepared from an isorneri/ed Fischer-Tropsch derived bottoms product.
- FT-4.1 , FT-4.3 and FT-7,9 had pour points such that the ratio of pour point, in °C. to the kinematic viscosity at 1 Of]°C, in cSt, was greater than a
- Base Oil Pour Factor where the Base Oil Pour Factor Is defined by the equation:
- AH of these base oil fractions also had traction c ⁇ ifieients less than 0,023 when measured at 15 cSt and at a slide to roll ratio of 40%.
- the l ' T-7,9, FT- 16 and FT-24 base o ⁇ !s had traction coefficients less than 0.017.
- FT-24 had an especially low traction coefficient of less than 0,01 1.
- the lubricant base oils having a traction coefficient less than 0.021 are examples of base oils that would he especially useful in gear lubricants to save energy. Examples of gear lubricants where significant energy savings would be achieved are heavy duty gear lubricants, EP gear lubricants, and worm ⁇ ear lubricants.
- Example S Example S:
- the blends additionally comprising a pour point depressing base oil blending component prepared from an isornerized Fischer-l ' ropsch derived bottoms product (GEARH and GEARJ) had lower Brookfield Ratios than GEARG which did not contain any.
- both of these comparative blends contained a higher amount of base oil (greater than 22 svt% of FT-S) has ing: a sequential number of carbon atoms, less than 40 wt% total molecules with cycloparaffmie functionality, and a ratio of molecules with inonocycloparafiinic functionality to molecules with mu ⁇ t ⁇ cyel ⁇ paiaffmie functionality less than 12.
- 3"T-S had a lower Vl than some of the other base oils useful in this invention.
- a base oil was prepared by hydroisomerization dewaxing a 50''5O mix of Luxco 160 petroleum-based wax and Moore & Munger CSO Fe-based FT wax.
- the hydroisomerized product was hydrofinished and fractionated by vacuum distillation.
- a distillate fraction was selected having the properties described in Table XI.
- FT-7.6 is an example of a base oil made from a waxy feed having a Vf greater than an amount defined by the equation:
- VI 28 x Ln(Kinemaiic Viscosity at IGO°C) + 105
- EHD film thickness data was obtained with an EHL Ultra Thin Film Measurement System from PCS Instruments, LTD. Measurements were made at 12O°C, utilizing a polished 19 mm diameter ball (SAE A1S ⁇ 52100 steel) freely rotating on a flat glass disk coated with transparent silica spacer layer
- FT- 7.95 was disclosed in U.S. Patent Application Publication Nos. 20050133408 and 20050241990.
- FT-14 and FT-16 were disclosed in patent application 1 1/296636, filed December 7, 2005.
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Abstract
Description
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11150097A EP2314664A1 (en) | 2006-04-07 | 2007-04-05 | Gear lubricant with a base oil having a low traction coefficient |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/400,570 US7425524B2 (en) | 2006-04-07 | 2006-04-07 | Gear lubricant with a base oil having a low traction coefficient |
| PCT/US2007/066080 WO2007118158A2 (en) | 2006-04-07 | 2007-04-05 | Gear lubricant with a base oil having a low traction coefficient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2024471A2 true EP2024471A2 (en) | 2009-02-18 |
| EP2024471A4 EP2024471A4 (en) | 2010-06-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP11150097A Withdrawn EP2314664A1 (en) | 2006-04-07 | 2007-04-05 | Gear lubricant with a base oil having a low traction coefficient |
| EP07760200A Withdrawn EP2024471A4 (en) | 2006-04-07 | 2007-04-05 | Gear lubricant with a base oil having a low traction coefficient |
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| EP11150097A Withdrawn EP2314664A1 (en) | 2006-04-07 | 2007-04-05 | Gear lubricant with a base oil having a low traction coefficient |
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| US (1) | US7425524B2 (en) |
| EP (2) | EP2314664A1 (en) |
| JP (1) | JP2009533496A (en) |
| KR (1) | KR20090010047A (en) |
| CN (1) | CN101437928B (en) |
| AU (1) | AU2007234769B2 (en) |
| BR (1) | BRPI0709854A2 (en) |
| WO (1) | WO2007118158A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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2006
- 2006-04-07 US US11/400,570 patent/US7425524B2/en active Active
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| EP2314664A1 (en) | 2011-04-27 |
| BRPI0709854A2 (en) | 2011-07-26 |
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| CN101437928B (en) | 2012-07-25 |
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| WO2007118158A2 (en) | 2007-10-18 |
| AU2007234769A1 (en) | 2007-10-18 |
| ZA200808113B (en) | 2010-02-24 |
| KR20090010047A (en) | 2009-01-28 |
| US7425524B2 (en) | 2008-09-16 |
| CN101437928A (en) | 2009-05-20 |
| JP2009533496A (en) | 2009-09-17 |
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